Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/06—Polystyrene
• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B13/00—Soles; Sole-and-heel integral units
  • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
  • A43B13/04—Plastics, rubber or vulcanised fibre
• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B13/00—Soles; Sole-and-heel integral units
  • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
  • A43B13/18—Resilient soles
  • A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

• the invention is related to a viscous polymer composition, a process for producing said viscous polymer composition, a composite comprising said viscous polymer composition, shoe soles comprising said viscous polymer composition or said composite, respectively, as well as the use of the viscous polymer composition or of the composite, respectively, for producing bodies, in particular shoe soles.
• GRF ground reaction forces
• Figure lb shows the subsequent pushing with the middle and front foot.
• the resulting vertical component of the GRF is depicted in Figure lc.
• the curve shows two significant force maximum.
• the first maximum appears after 20 - 30 milliseconds (ms) caused by the hit of the heel.
• said force maximum is usually referred as "impact- force-maximum” since the human body does not react and adapt during said short interval.
• the second force maximum appears after 60 ms to 80 ms and is caused by the push.
• Said force-maximum is usually referred as "active-force-maximum” or "push-force-maximum”.
• Impact-forces do nothing to the forces of the athlete. Impact-forces have been considered to be relevant with respect to chronic and degenerative injures of several sports, in particular when the heel is involved. It is therefore one object, to reduce impact-forces by employing suitable constructions for shoe soles. Systems are intended, which easily deform under force and also disperse the energy.
• the amount and the duration of the active forces determine the performance of the athlete, i.e. the running force and the jump heights. This means that a certain provision of active forces has to be saved, when the athlete intends to run a certain speed. It is therefore intended to support such forces. N shoe sole can influence this, which minimizes the energy dispersion as much an possible and generates the necessary suppression at the same time.
• a sole unit consisting in a running sole and a inter- mediate sole, being fixed thereon.
• the intermediate sole is defined by a relatively small, frame-like circulating strip, which defines a unit, which is closed on its lower end by the running sole.
• Said unit carries two sole parts. One of those sole parts starts at the front foot area and ends at the beginning of the heel, where the second sole part is located.
• the first sole part consists in a polymer support inlet which has a relative high elasticity when pressure is applied, in a way that during walking with said shoe a foot bed can result on the sole part, which guarantees a certain comfort.
• the sole part which is located in the heel area builds a shock absorber and consists in shock absorbent, viscous material like sili- cone.
• US-A-4,910,886 describes the use of shock absorbing inlets made of viscous material in the heel area of a sole unit.
• US-A-4,316,335 discloses the use of a viscous shock absorbing material in the front part of a sole as well as in the heel part, wherein the shock absorbing properties in the heel part should be better.
• a shoe sole wherein in a layer composition the viscous material which is a polymer composition is implied as one possible layer.
• Said polymer composition consists in a cross-linked ethylene- vinylacetate copolymer (referred as EVA) and for increasing the tensile strength and other material properties, for example styrene-butadiene-rubber.
• EVA cross-linked ethylene- vinylacetate copolymer
• silica gel is implied as a filler and furthermore the usual aids for cross-linked rubber are used.
• the object of the present invention is to provide a viscous material, in particular suitable for the passive and active force maximum occurring during the natural movement and which optimally uses a natural movement dynamic and thus provides a safe and efficient forward movement of the runner. Moreover, it is desired that the viscous material can be used without bigger adaptations in known plants for producing shoe soles in a efficient and cheap manner.
• a viscous polymer composition which comprises and in particular contains:
• a halogen comprising polymer D obtainable from at least one C 4 - to Cio-diene and at least one halogen;
• the polymer composition according to the invention can contain the usual aids and additional compounds as for example to simplify removing the polymer composition from a mould.
• component A All possible combinations of the component A with the components B - E are preferred according to the present invention.
• component B can be combined with the components C to E.
• preferred combinations of the components are given by the following letter combinations: AB, AC, AD, AE, AEC, ABCD, BC, ABC, ABCDEF and NBCDE.
• viscous polymer composition which contains components:
• polymer A 0 to 99.9 wt-% polymer A, preferably 5 to 60 wt-%,
• polymer B 0 to 99.9 wt-% polymer B, preferably 5 to 60 wt-%,
• polymer C 0 to 99.9 wt-% polymer C, preferably 5 to 60 wt-%,
• the amount of component F if present is up to 15 wt-%, preferred from 0.5 to 5 wt-% in relation to the remaining polymer composition.
• C 4 -C 8 - and in particular preferred C -C 6 - and moreover preferred C 4 -C 5 -dienes are employed as monomer Al.
• C 4 - C 5 -dienes are preferably butadiene and isoprene, wherein butadiene is in particular preferred.
• C 8 -C ⁇ - and particularly preferred C 8 -C ⁇ 0 -monomers are employed as monomer A2.
• ⁇ -methylstyrene and styrene are preferred and styrene is in particular preferred.
• Polymer A is preferably a block polymer, which comprises at least one block of monomer Al and one block of monomer A2.
• a block polymer which comprises at least one block of monomer Al and one block of monomer A2.
• a three block copolymer with on block of monomer A2 followed from one block of monomer Al again followed by one block of monomer A2.
• a poly-(styrene- butadiene-styrene)-block copolymer as for example available under the trade name Styroflex® by BASF AG is in particular preferred.
• Such poly-(styrene-butadiene-styrene)-blockcopolymers consist of "islands" of polystyrene as a hard fiber which are bedded in a matrix of rubber-like statistical styrene-butadiene-copolymer which makes the material flexible.
• these materials have a shore A-hardness (3s)15s, according to DIN 53505 in a range of (85 to 90) or 80 to 85 respectively.
• the shore D-hardness (3s)15s, measured according to DIN 53505 is in a range of (30 to 35) or 27 to 32 respectively.
• Such materials have a low glass transition temperature in the range around -40°C and a breaking temperature (according to DIN 53372) in a range of approximately -35°C. Further information about this material is given in the data sheets concerning Styroflex®, obtainable from BASF AG, Ludwigshafen.
• Polymer B is a copolymer at least formed from the monomers Bl and B2.
• the monomer Bl is preferably a C 2 - to C 20 - more preferably a C 2 - to - and in particular preferable C 2 - to Cio-olefm. It is moreover preferred that monomer Bl is an alpha-olefin.
• ethylene, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene and 1-nonene are preferred and ethylene as in particular preferred.
• Monomer B2 being further employed in polymer B, is the product that is for ex- ample obtainable from a vinyl alcohol, in particular with 2 to 8 and more particular with 2 to 5 and even more particular with 2 carbons and a carboxylic acid with particular 2 to 8 and more particular 2 to 5 and even more particular 2 carbon atoms.
• Polymer B can contain polymer B2 in a range from 5 to 25 and particular from 15 to 23 wt-%.
• polymer B is ENA(ethylene-vinylacetate)-polymer with a vinyl acetate content of 18 to 21 wt-%, based on the total polymer B in the vis- cous polymer composition according to the present invention.
• This EVA-polymer is supplied for example by Leuna Polymer GmbH, DuPont or Exxon.
• the content of vinylacetate as well as the melting index of the copolymerisation determine amongst others the mechanical and thermal properties of the polymer.
• elongation, tension-tear stability, flexibility, cold resistance, rebound elasticity, tolerance and stickyness increase whereas hardness, stiffness, elasticity, vica temperature, bending stress and resistance towards chemicals decrease.
• Polymer C is a polymer, obtainable from at least one vinylaromatic monomer, like for example styrene. Generally, such polymers are liquid in a temperature range from -10 to 100°C. Preferably, polymer C is liquid in a range from 0 to 70°C, especially preferred from 10 to 50°C.
• a C to Qo-diene reference is made to the explanation concerning monomer Al .
• the halogens in polymer D are preferably fluorine, chlorine and bromine and in particular preferred bromine.
• conjugated dienes employed in polymer D reference is made to monomer Bl.
• bromo butadiene bromo ispoprene are preferred and bromo butadiene is in particular preferred. Accordingly, poly bromo butadiene rubber is in particular preferred as polymer D.
• filler E all fillers know by the person skilled in the art can be used.
• fillers can be divided in inorganic and organic fillers.
• inorganic fillers are preferred.
• Said fillers particularly base on Si wherein silicon oxide are more preferred and silica is mostly preferred.
• the use of fillers also increases the abrasion resistance of the viscous polymer composition.
• fillers to be mentioned are for example: soot, calcium and aluminium silicates, aluminium oxide, kaolin, silica, french chalk, chalk and metal oxides, like for example zinc oxide and metal carbonates.
• inorganic and organic pigments can be used as fillers, wherein pigments of titan oxide, zinc sulfide, iron oxide, chromium oxide, cad- mium and chromate are preferred as inorganic pigments, and as organic pigments are especially preferred: diarylic- and pyrazolon-diazopigments, pigments of the ⁇ -naphtholcarboxylic acid or ⁇ -naphtholcarboxylic acid-arylits, derivatives of naphthalenetetracarboxylic acid or derivatives of peryleneteracarboxylic acid, pigments of dioxazine as well as pigments of chinacridon condensation products, thioindigo-isoindolinone condensation products and diazo condensation products.
• Aids are in particular activators, inhibitors, plasticizers, cross-linkers, separating agents, softeners and blowing agents in the case that the viscous polymer composition is a foam.
• Activators can be inorganic or organic compounds. According to the present invention it is preferred that the viscous polymer composition contains a organic and an inorganic activator. Fatty acids are preferred organic activators, wherein sterenic acid is in particular preferred. Inorganic activators are in particular oxides of transition metals, wherein zinc oxide is in particular preferred.
• separating agents to the viscous polymer com- position.
• the separating agents known to the person skilled in the art can be employed.
• suitable are separating agents which are a salt of a fatty acid and a transition metal, wherein zinc stearate is in particular preferred.
• softeners in the viscous polymer composi- tion according to the present invention.
• Suitable softeners are known by the skilled person. Phthalates, adapenic acid ester and polyesters with rather low degree of polymerization are preferred. From these phthalates are in particular preferred, wherein di-octyl phthalate is in particular preferred in the viscous polymer composition according to the present invention.
• blowing agents can be used which are known to the person skilled in the art. Preferred blowing agents are halogen free carboxylic amides as for example the product NDC K from Fa. Bayer AG or AC3000H.
• the viscous polymer composition according to the present invention can be produced by a process, wherein the above mentioned components are brought into contact. Injection moulding is a preferred method for processing the polymer composition.
• the viscous polymer composition according to the present invention is obtainable by bringing the above defined components into contact.
• the viscous polymer composition according to the present invention comprises at least one of the following material properties:
• An energy loss in the range of 50 to 80 preferably from 55 to 75 and more preferably from 60 to 70%, a stiffness at 200 ⁇ to 400 ⁇ in the range of 80 to 150, preferably of 100 to 140 and more preferably of 110 to 130 ⁇ /mm, a stiffness at 1000 ⁇ to 1500 ⁇ in the range of 100 to 400, preferably of 150 to
• the polymer composition according to the present invention can have all possible combinations of the single properties a) to e).
• Preferred property combinations of the viscous polymer composition according to the present invention are given in the following letter combinations: ab, abc, abed, abcde, be, de, ac, ad, ae, ace, be, bd, and ce.
• the invention is related to a composite, comprising or preferably consisting in a viscous polymer composition according to the present invention and an elastic material.
• the elastic material of the composite has at least one of the following properties:
• the elastic material of the composite can have the above defined properties ⁇ ) to ⁇ ) in all possible combinations.
• the following combinations are more preferred: ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ .
• An elastic material in the composite with all the properties ⁇ ) to ⁇ ) is most preferred.
• the viscous polymer composition VI and the elastic material V2 are directly adjacent to each other. This is in particular preferred when the composite only consists in the viscous polymer composition according to the present invention and the elastic mate- rial.
• the viscous polymer composition VI and the elastic material V2 are separated at least in one part by at least one further material V3. Said composite preferably consists in the viscous polymer composition VI, the elastic material V2 and a further material V3.
• the elastic material V2 can be made of all suitable materials, in particular elastic polymers, known by the skilled person.
• the further material V3 differs from the viscous polymer composition VI and the elastic material V2 in at least one material property, wherein the further material V3 preferably also differs with respect to its composition from the viscous polymer composition VI and the elastic material V2.
• the invention is related to a body, in particular a shoe sole, inlays for shoes, protectors, especially for elbow and shin, and shoulderpads, comprising, preferably consisting a viscous polymer composition or a composite according to the present invention.
• the invention is rated to the use of a viscous polymer composition or a composite according to the present invention for producing of bodies, in par- ticular shoe soles.
• the viscous polymer composition according to the invention can be used to produce bodies in the whole area of healthcare and medical applications like for example health-shoes, orthopaedic shoes, orthopaedic inlays or elbow- pads.
• body generally means forms, foils, fibers, films and coatings. Bodies are preferred in which the properties of the viscous polymer composition or the composite according to the invention or both are favorably applicable. 5. Brief description of the drawings
• Fig. 1 The natural movement of the foot during running ( Figures la to b) and the resulting GRF-force profile (Fig. lc);
• Fig. 2a N force-time-diagram of two force fields, which are applied from a measuring device according to the present invention on the heel area and the front foot area of a sole unit according to the present invention or material layers, respectively, to determined the energy loss according to the present invention and the dynamic stiffness;
• Fig. 2b a measuring device according to the present invention used for applying the force profile according to Figure 2a and for measuring the resulting de- formation (and thus the energy loss and the dynamic stiffness);
• Fig. 2c The force stamps used in a device according to Figure 2b for the heel area and the front foot area;
• Fig. 3 the deformation behavior of a viscous material with a resulting energy loss (hatched) and the dynamic stiffness DS between 1 Kn and 1.5 K n
• Fig. 4 the deformation behavior of elastic material with the resulting energy loss (hatched) and the dynamic stiffness (DS between 1 Kn and 1.5 Kn);
• Fig. 5 a sole layer according to the preferred embodiment of the present invention, wherein in the front foot area an elastic material is used and in the heel area a viscous material is used;
• Fig. 6a a cross-sectional view of an embodiment of the composite according to the present invention or a cut along the line A-A (or B-B, respectively), of the preferred embodiment shown in Figure 5;
• Fig. 6b a cross-sectional view of an embodiment of the composite according to the present invention or a cut following the line A-A (or B-B, respectively), of the embodiment of Figure 5.
• Figure 1 depicts a human foot with a shoe 10 which essentially consists in a shaft 20 and a sole unit 50.
• the sole 50 preferably consists in a plurality in layers which is further referred to as layer assembly.
• the GRF-curve has a first sharp maximum after 25 ms which results from a fast increasing force, which is equivalent to 2.5 times weight force as shown in the example of Figure lc. As already addressed in the introduction, this maximum is also referred to as vertical force impact peak-value (VFIP- value).
• VFIP- value vertical force impact peak-value
• the GRF- diagram After the passive phase of moving the so-called active phase follows in the GRF- diagram.
• the second force increase in the active phase results from the push of the foot from the ground (reference is made to Figure lb).
• the stroke on the moving apparatus resulting from the active phase is much lower since a force appears slower compared to the active phase (approximately 60 to 70 ms).
• the GRF- diagram is strongly dependent from each single case and the conditions involved (running speed, anatomy of the foot, hardness of the ground, etc.).
• the load of the front foot area is lower. Furthermore, said front foot area has a bigger surface and an anatomic form, which allows a better absorption.
• the sole has the property, wherein the component of the moving energy directing in the running direction is released as schematical energy in running direction and/or from the ground. Again, reference is made to Figure lb in this respect. If during the contact of the front foot with a ground genetical energy is again transferred to the foot, this yields in a reflection of the foot from the ground and thus, supporting the forward movement.
• the present invention is thus based on the result that in the heel area and in the front foot area of a sole unit materials with different properties should be used:
• In the front foot area it is preferred to use an elastic material.
• This property (measured in %) describes the ratio of the energy applied to the material over the occurring force field to the energy obtained by relaxation.
• Said device consists in a platform 5, with the material to be measured thereon.
• Said material can be a single material layer (preferred) or - as shown - a sports shoe. In each case, it is preferred that the investigated material is used with the same thickness and in particular in one of the same form, in which it is used in the shoe later on.
• a defined force field is applied by the stamp device 7 via a stamp 8 (as to be de- scribed bellow) (compare Figure 2c).
• a stamp 8 as to be de- scribed bellow
• stamp device 7 The build up of the stamp device 7 and the measuring device 6 is well-known to the person skilled in the art. Besides the stamp 8 being described below such a device is commercially available under the name INSTRON UNIVERSALL 8502 of the company INSTRON Wolpert GmbH, Ulm.
• stamp 8a is used for the test of the elastic and viscous materials to simulate reality as much as possible. Accordingly, for the testing of suitable viscous polymer a force field is applied, which is called “heel” in Figure 2a. To be as close to reality as possible, furthermore, stamp 8a is used.
• the geometry of said stamp is equivalent to the human heel. Stamp 8a has a circular cross-section with a diameter of 5 cm and a cross-sectional area at the lower end of 19.63 cm 2 (which is slightly curved).
• front foot is used for measuring elastic materials.
• the stamp 8b is in said measurements as adapted to the geometry of the human front foot.
• Stamp 8b has a lengthy form with a length of a 8.5 cm and is 5 cm broad. It is also (slightly curved). The lower side has a cross-sectional area of 42.50 cm . Finally, the materials are examined with a thickness which usually occurs in shoes (10 mm in the front foot area; 20 mm in the heel area).
• FIG. 3 the deformation behavior of a viscous polymer composition is shown. Said deformation behavior is obtained with the device of Figure 2b and with a force profile "heel" in Figure 2a, wherein the abscesses shows the deformation measured with device 6 depending on the force field applied with stamp 7. Said Figure shows that the viscous polymer composition according to the present invention which is preferably used in the heel area shows a strong hysterese behavior.
• the force according to the force profile "heel” as shown in Figure 2a a deformation is obtained which relaxes slowly and with a significant lower counter force on stamp 8a.
• Said energy loss can be obtained graphical or numerical and is shown by the hatched area in the diagram.
• the diagram shows a significant part of the energy applied to the viscous polymer composition according to the present invention is changed into heat and is not available any more in the material when this relaxes to its original form.
• the diagram from Figure 3 shows besides the energy loss a further parameter which is important for the present invention, i.e. the dynamic stiffness (DS) of the tested materials.
• the dynamic stiffens is defined as the ratio between the applied force F (N) and the resulting movement d (mm).
• N applied force
• mm resulting movement
• Said ratios can be calculated as follows:
• Dynamic stiffness DS 1000-1500 (FISOON - FIOOON) (disooN - diooor [N/mm]
• the value of dynamic stiffness between 200 N and 400 N can be also calculated according to the above equation. Said value is not shown graphically in Figure 3.
• the dynamic stiffness is according to the present invention of interest of a sole unit which is a layer assemble (i.e. a plurality of layers from different materials).
• a layer assemble i.e. a plurality of layers from different materials.
• Said assemblies show the above described effect according to the present invention only if the stiffness of the function layer is not higher than the stiffness of the materials of which the layers are made.
• Figure 4 shows the behavior of a preferred elastic material.
• the elastic material only shows a weak histerese behavior and thus only a very small energy loss. The material relaxes almost simultaneously when the force is reduced, wherein almost all the energy provided by force stamp 8b is released.
• the value for a dynamic stiffness between 1500 N and 1000 N is shown (the corresponding value for the dynamic stiffness between 400 N and 200 N is again not shown).
• the dynamic stiffness of the elastic material between 1000 N and 1500 N should be less than 450 N/mm and the dynamic stiffness for the viscous polymer composition should be less than 200 N/mm.
• the dynamic stiffness of the elastic materials between 1000 N and 1500 N should be less than 600
• the dynamical stiff- ness of the viscous polymer composition between 1000 N and 1500 N should be less than 250 N/mm and between 200N and 400N less than 130 N/mm.
• Figures 5 and 6 show preferred embodi- ments of soles according to the present invention.
• Figure 5 is a horizontal cut through a sole according to the present invention.
• a running sole 50 of a shoe 10 shown which is divided in a front foot area 60 and a heel area 80.
• the sole 50 itself can be a plurality of single layers as it is usually the case for sport shoes.
• the sole can consist in an outer sole 55 and a middle sole 59 and not shown in a sole (compare Figure 6a).
• a function layer 57 there is between the outer sole 55 and the middle sole 59 a function layer 57.
• Said function layer 57 can be divided in two horizontal areas, i.e. the front foot area 60 with elastic material and the heel area 80 with the viscous polymer composition. Between said two horizontal areas there can be a transition area 70. The front foot area 60 and the heel area 80 can also be in contact.
• first function layer in the front foot area comprises the elastic material and the second function layer in the heel layer comprises the viscous polymer composition.
• the functional layer 57 can extend a little bit or a lot towards middle sole 59 (Figure 6a). This depends on the application of the sport shoes. In cases, where the probability of the laterally hitting the ground is high (sports with jumps) the embodiment according to Figure 6b is preferred. However, the embodiment according to Figure 6a is for example applied to running shoes.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=7633243

Family Applications (1)

Country Status (6)

Families Citing this family (23)

Family Cites Families (41)

• 2000
  • 2000-03-02 DE DE10010182A patent/DE10010182B4/de not_active Expired - Lifetime
• 2001
  • 2001-03-02 JP JP2001564278A patent/JP2003525334A/ja active Pending
  • 2001-03-02 US US10/204,800 patent/US20050065270A1/en not_active Abandoned
  • 2001-03-02 DE DE60122302T patent/DE60122302T2/de not_active Expired - Lifetime
  • 2001-03-02 EP EP01911724A patent/EP1268663B1/de not_active Expired - Lifetime
  • 2001-03-02 AT AT01911724T patent/ATE336549T1/de not_active IP Right Cessation
  • 2001-03-02 WO PCT/EP2001/002403 patent/WO2001064787A1/en not_active Ceased

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events